Recovery of metallic oxides such as zirconia



Patented Dec. 18, 1951 RECOVERY OF METALLIC OXIDES SUCH AS ZIRCONIA Robert A. Schoenlaub, Cleveland, Ohio, assignor to Sylvester & Company, Cleveland, Ohio, a corporation of Ohio No Drawing. Application March 25, 1946, Serial No. 657,057

3 Claims.

The present invention relates to the recovery of zirconia from its ores and minerals. More particularly it relates to a direct process for obtaining the stable form of the oxide. The advantages and novel features will be apparent from the following description.

Zirconia is a potentially useful substance. It has a melting temperature of about 4900 F. and a considerable resistance to slags of widely varying character. Also, it has a high index of reprocess of separating an amphoteric oxide from a fraction and is hard and tough; so that it can be compound of such an oxide which comprises furused as opacifiers, pigments, or abrasives. It nacing the material under such conditions as to can also be used as a starting point to form zirform a friable silicate whose crystalline structure conates, titanates, silicates, and the like, which has pronounced cleavages and anoxide of said have unusual and useful properties. 5 metal, comminuting the-smelted mass and then Zirconia is not extensively used, although its separating said oxide therefrom. ores and minerals are plentiful and relatively It will thus be seen that my invention cheap. The conversion of zirconia materials to prises a simple process by which amphoteric the oxide has heretofore been extremely difiicult. oxides may be obtained directly from their min- It has been prepared by volatilizing of silicon in erals. The process of this inventionmay be illusthe high temperatures of the arc furnace. Also trated by havin particular reference to the reit has been brought into solution in various ways, covery of zirconia. such as fusion with caustic alkalies, or carbonates, The process consists of two essential steps: or with fluorides and subsequent acid dissolution. First the zirconia raw material is furnaced in a The impurities have then been separated by comchemical and physical environment which causes Plicated and exacting processes involving pr cipi the crystallization of Zirconium oxide in discrete tation, solution, and washing to obtain zirconium rain and i a tab1e and/or relatively pure sulfates, hydroxides, and the like. These comform; secondly, the zirconia is separated from the pounds have then required further furnacing at a undesirable gangue by a process of comminution high temperature to convert them to a refractory d supplementary t t t, Th supmemen; grain. Such processes are far too expensive to tary treatment is preferably by ore dressing techsatisfy the potential industrial needs, and produce niques such as classification, tabling, flotation, or an oxide which is physically and thermally unthe like; but it may be chemical dissolution of the stable. waste matter; or it may be by a rougher separa- While my invention as above indicated is con- 5 tion by physical means followed by a simple cerned with the recovery of zirconia from its ores chemical cleaning operation. and minerals, nevertheless, the process compris- There are several novel features in my invening my invention will be found applicable to the tion. Previously zirconium minerals have been recovery of amphoteric oxides. By amphoteric furnaced so that the ZIOz becomes susceptible to oxides as used in this description andin the ap- 41') chemical solution. I furnace such minerals so pended claims, I mean refractory oxides which that the zirconia becomes refractory to chemical are less basic than magnesia and less acid than solution. Also, purification was previously a mati ter of chemical solution and precipitation; where- It is a principal object of my invention to proas I employ mineral dressing techniques. Also, vide a simple process by which zirconia may be 5 previously the zirconia was obtained in an unobtained directly from minerals. stable form; whereas I can obtain it directly in a It is a further object of this invention to prohi h mp r u stable d r la f rm- A vide a process which because of the simplicity still further novel feature is that previous procand low cost of the materials used may be peresses opera e better on la v ly p r w m formed with such yields that the cost of the zirterials; whereas my process Works better on comconium oxide produced thereby is much lower para ve y impure materials Other distinctive than any production costs heretofore available. features and advantages o my melhod W111 be Other objects of my invention will appear as pp from the folloWmg descriptionthe description proceeds. I usually will use zircon as a raw material.

To the accomplishment of the foregoing and re- The mineral contains about mm and the related ends, said invention then comprises the features hereinafter fully described and particularly pointed out in the claims, the following description setting forth in detail certain illustrative embodiments of the invention, these being indicative, however, of but a few of the various ways in which the principle of the invention may be employed.

Broadly stated, this invention comprises the mainder is largely silica, which conforms closely with the formula ZIOz-SiOz. Some zircon sands will contain ilmenite, rutile and monazite, but such impurities serve a useful fluxing function in my process and need not be removed. I may also use other materials such as impure baddeleyite (Zr02) or zirkite, which is a mixture of baddeleyite and zircon; but all such I will henceforth refer to as zircon.

The first step in my process is the furnacin'g of zircon with other substances which preferentially combine with the undesirable matter, thus freeing zirconia. All monovalent, divalent, and tri valent basic oxides such as K20, Na20, BaO, SrO, CaO, Mgand A1203, etc., seem to have the power of displacing zirconia from zircon if used in suitable combinations and amounts. However, as the possible systems are extremely complex and refractory, it is most convenient in explaining my invention to give examples of suitable combinations and amounts.

It is perhaps easiest to consider the substances and combinations which may be used from the standpoint of the end products which form. Zirconia will not exist in the presence of acid silicates such as feldspars. It is usually compatible with the common metasilicates, as for examplepyroxenes; intermediate silicates, as for examplemelilite; and orthosilicates, such as the olivenes. In extremely basic systems, zirconia will react to form zirconates and in extremely acid systems it forms zirconium silicates and with alkalies it will form alkali zirconium silicates. There are, however, wide ranges of composition through which it can be made to form in the manner desired.

In general the ranges of composition useful with my invention can be defined as compositions of matter which react to form friable silicates such as the metasilicates, melilites, or orthosilicates, or combinations thereof, and zirconia. Alternatively they may be defined as compositions of matter in which the basic functioning oxides and acid functioning oxides are in ratios of between l:l and 2:1.

The preferable oxides which I may add to zircon are 09.0, MgO, A1203 or combinations thereof. These will produce displacement of the zirconia according to the following typical reactions:

I. Reaction of basic oxides with zircon to form metasilicate and zirconia:

II. Reaction of basic oxides with zircon to form melilites and zirconia:

2(Zr02-Si02) plus ZCaO plus Mg0- 2CaO-Mg0-2SiO2 plus 2 (Zr02) Zr02-Si02 plus 2Ca0 plus A1202 2CaO- AlzOs SiOz plus ZrOz III. Reaction of basic oxides with zircon to form orthosilicates and zirconia:

Zr02-Si02 plus 020 plus Mg0- Ca0-Mg0-Si02 plus Zr02 Zr02-Si02 plus 2Mg0 2MgO-SiO2 plus Zr02 It must, however, be recognized that these are examplatory and the minerals formed may be more complex than indicated. As examples pyroxenes may contain ferrous and ferric oxide, sodium oxide, manganese oxide, titania, fluorine, etc. The melilites and orthosilicates similarly are complex. Their nature can best be determined from any standard textbook on mineralogy. Typical batches and calculated chemical and mineralogical compositions which I may use to obtain the zirconia from zircon are as follows:

Chemical Composition CaO per (clentn 1 Mineral Composition Diopside (CaO-MgO-2SiO2) per cent 49.2 33.8 Akermanite (2CaO-MgO-2Si0z). do.... 45.1 4.3 41.3 Gehlenite (ZCaO-AlzOa-SiOz) per cent" 71.0 Monticcllite (CaO-Mg0-SiO2) percent. 14.0 15.3 57. Zl100Dl3.(Zl0z) do. 50.8 54.9 48.0 43.6 42.5 29.0

It will be found preferable to adjust the composition by suitable additions so that a major part of the silica reacts to form melilite. Melilite is a continuous series of solid solutions between gehlenite (2Ca0-Al20sr'3i02) and alrermanite (2CaO-Mg0 28102) but as mentioned, it also may be ery complex in composition. This preference is due to the fact that the melilites are easily fused. They are great scavengers when used in slags, as for example in the blast furnace, and they have a crystal structure and cleavage which facilitates separation. Preferably the remainder of the silica can be combined either as diopside (CaO-Mg0-2SiO2) or clinoenstatite (Mg0-Si02) or both. Batching is not critical, but the impurities should be considered if they are excessive in amount or unusual in character. Relatively pure materials such as baddeleyite may be handled by adding silica to provide the necessary scavenging action and then treating as with zircon.

Composition must be given additional consideration in cases in which it is desired to obtain the unstable form of the oxide, or to obtain the oxide in a purer form than is the usual case. This will be subsequently discussed.

The melting process is quite simple. The raw materials are crushed to -l0 mesh, mixed in the desired proportions, and inserted in a suitable furnace. The batch is then fused and finally held at about 29-00 F. for about six hours or until the H02 crystals attain a size and uniformity suitable for the separation process. The slag is then poured and allowed to cool. As in other ceramic processes, there is considerable latitude in the furnacing. This can be accomplished at comparatively low temperatures if the time is sufiiciently long, or it can be accomplished in short periods of time if the temperature is sufficiently high.

Any reverberatory, electric furnace or similar device, which is capable of reaching the requisite temperatures may be used. The requisite temperatures are above 2600 F. The furnace should have a tipping device and large pouring ports or spouts so that the removal of the viscid Zr02 containing slag is facilitated. The hearth material which may be used is somewhat dependent on the composition of the melt. In the. more acid melts the hearth may be fireclay; in some of them it might be chromite; and with the more basic fusions, it may be magnesite. With all such refractories there will be'some corrosion of the hearth, particularly of the slag line and also some undesirable contamination of the slag. A successful practice is to build a fireclay subhearth and to fettle this with a zircon-limestone mixture of the same basic oxide to silica ratio as used in the batch.

.When thus smelted, the fused slag will comprise sphericalparticles-of. ZIOz in a matrix of crystallized silicate. The size and uniformity of the crystals will depend upon the intensity of firing; high temperatures, and prolonged firing will give better uniformity and size.

The separation of the silicate gangue from the ZIOz crystals is a simple process, comprising the following steps: Crushing, grinding, classification, and/or flotation, and/or chemical cleaning.

The actual details'of the processing will depend.

upon the size and uniformity of the crystals obtained and the degree of separation required. Also, the grinding, classification, etc. may be wet or dry or any combination thereof.

Comminution can be obtained by any conventional crushing, and screening system as for example, a primary jaw crusher and an intermediate gyratory crusher operating in a closed circuit with a circulating load. The crushed screened product can then be fed to a rod mill and classifier to produce a product substantially of 70 mesh or otherwise suitable for a ball mill feed.

The final grinding is the only critical part of the process. In this step the fines previously reduced are ground so that the tough spherical ZrO2 grains are freed from the siliceous gangue, without crushing, and the friable silicates are reduced to extremely small sizes. This grinding can be conveniently accomplished in a pebble mill using small pebbles and long grinding periods. After comminution the product will be found tucomprise ZrO2 crystals, more or less spherical in shape, and about 30 microns in size, and silicate fines of about 5-10 microns in size.

The simplest means of separating the gangue from the ZrOz is by classification. Separation by classification is favored by the specific gravity of ZrO2 (about 5.6) and of the silicates (about 3) and by the tabular and acicular shape of the silicates which are subsequently described. It can also be favored by the use of high temperatures in firing so that comparatively large and uniform ZrOz crystals are obtained and careful grinding so that fine silicate grains are obtained. The classification can be made by the continuous centrifuge with the cut taken at about 15 microns.

Alternatively I may use flotation as a means of separation. It is somewhat difiicult to preferentially float Zl'Oz, but it can be done to some extent by the use of cationic amines. It is usually easier to float 01f the silicates by fatty acids, their derivatives, such as sodium oleate, or sulfated alcohols. The flotation is preferably done in a thin slurry and the slurry activated with a lead salt. Such a flotation will remove the bulk of the silicates, leaving the ZIO'2 grain.

The physical or chemical separation process of the kind described will not give a complete separation. Usually the ZI'Oz grains will have from 5 to attached or otherwise associated matter. This can be removed chemically. The contaminated grains are merely added to muriatic acid-and digested until the silicates are destroyed. The suspension is diluted with water and washed free from chlorides. The grain will then be associated with tenacious silica gel. This can be removed by adding causticsoda and agiform exists in several polymorphous'modification's, somewhat likesilica and titania. The natural form, baddeleyite is monoclinic. 'At atempcratureof about 1800 F. it inverts to a tetragonal' form with a marked contraction in volume. This inversion is reversible and the volumetric instability so caused prevents the use of the oxide in formed refractory shapes. A stable cubic form can be made by the absorption by solid solution of the oxides of calcium, magnesium, scandium, yttrium and cerium, as well as beryllium and others in amounts of 2 or more percent. In the practicedescribed, the stable form is usually obtained.

If zirconiafor chemical purposesor the unstable form isotherwise-desired, it can be made by a modification of 'th'is"process. way to accomplish this is by adjusting the slag composition so that the silicates are of the acid or metasilicate type; for instance, for each two molar equivalent-of silica, a molar equivalent of dolomite should beadded and the silica removed as diopside. Another-way of making the unstable oxide is by use of cxides which-have no stabilizing effect, to form the silicates. Conversely on occasions I may add stabilizing oxides 01' minerals to the slag for the purpose of improving the stability.

The operability of the process depends largely upon the pronounced cleavages possessed by the silicates. The pyroxenes have a prismatic cleavage which gives acicular fragments. The orthosilicates have pinacoidal cleavages (010, 001) which give blocky rectangular grains. Melilites are tetragonal with an extremely pronounced basal cleavage which gives mica-like fragments. As ZrO2 has no observable cleavage and occurs in spherical grains, attrition in the mill will roll the grain and shear it free from the friable silicates. The separation is quite easy with melilites, less easy with pyroxene, and somewhat more difiicult with the orthosilicates. Chemical separation is easiest with the orthosilicates, less so with the melilites, and most difiicult with the pyroxenes. However. in no case does the chemical stability of the silicates approach that of the zirconia.

As previously indicated, this invention is applicable to other oxides. In general, it may be used for the extraction of any amphoteric refractory oxide which is in equilibrium with a silicate melt in which the ratio of basic functioning oxides is to acid functioning oxides as from 1:1 to 2:1. In some instances the operation of this invention will require the addition of basic oxides; in others, acidic oxides such as silica; and in still others, both acidic and basic oxides. Particularly my invention applies to the extraction The "easiest of beryllium oxides from beryl; thorium bxide from its silicates; and chromium oxide from chromite.

The following is a typical batch as one example of my invention:

Parts Limestone (10 mesh) 16.25 Calcined magnesite (10 mesh) 3.75 Zircon (sand) 27.5

until the siliceous gels were dispersed from the zirconia grain. I then separated the gels and the grain by again classifying. Final washing and de-watering gave ZrOz sand.

From the description previously given of the general process, those skilled in the art, by following the procedure outlined above in the representative example, will be able to carry on the process with such modifications as are required for particular materials.

Other modes of applying the principle of the invention may be employed, change being made as regards the details described, provided the features stated in any of the following claims or the equivalent of such be employed.

I therefore particularly point out and distinctly claim as my invention:

1. A process for recovering zirconium in the form of zirconium oxide from a substance containing a silicious compound of the metal which comprises forming a heterogeneous system of discrete crystals of zirconium oxide and a crystalline silicate gangue substantially free of such oxide by heating and reacting said material at a temperature below about 3200 F. with an added basic material in such an amount that the basic functioning oxides and acid functioning oxides are present in ratios of between 1:1 and 2:1 and which basic material is of such type that upon reaction with silica in the stated proportions will produce preponderantly soluble ortho-silicates thus setting free the zirconium oxide as such in crystal grains and forming a friable sili-'- cate gangue, and after disintegrating the mass, separating the ortho-silicate thus formed from the zirconium oxide grains.

2. A process in accordance with claim 1 characterized further in that said added basic material contains a substantial proportion of calcium oxide.

3. A process in accordance with claim 1 in which said added basic material contains a substantial proportion of magnesium oxide.

ROBERT A. SCHOENLAUB.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,340,888 Gordon May 25, 1920 2,076,080 George et a1 Apr. 6, 1937 2,084,630 Deguide June 22, 1937 OTHER REFERENCES Floatation and Agglomerate Concentration of Non-Metallic Minerals, Bureau of Mines Report of Investigations, May 1938, pages 19 and 20. 

1. A PROCESS FOR RECOVERING ZIRCONIUM IN THE FORM OF ZIRCONIUM OXIDE FROM A SUBSTANCE CONTAINING A SILICIOUS COMPOUND OF THE METAL WHICH COMPRISES FORMING A HETEROGENEOUS SYSTEM OF DISCRETE CRYSTALS OF ZIRCONIUM OXIDE AND A CRYSTALLINE SILICATE GANGUE SUBSTANTIALLY FREE OF SUCH OXIDE BY HEATING AND REACTING SAID MATERIAL AT A TEMPERATURE BELOW ABOUT 3200* F. WITH AN ADDED BASIC MATERIAL IN SUCH AN AMOUNT THAT THE BASIC FUNCTIONING OXIDES AND ACID FUNCTIONING OXIDES ARE PRESENT IN RATIOS OF BETWEEN 1:1 AND 2:1 AND WHICH BASIC MATERIASL IS OF SUCH TYPE THAT UPON REACTION WITH SILICA IN THE STATED PROPORTIONS WILL PRODUCE PREPONDERANTLY SOLUBLE ORTHO-SILLICATES THUS SETTING FREE THE ZIRCONIUM OXIDE AS SUCH IN CRYSTAL GRAINS AND FORMING A FRIABLE SILICATE GANGUE, AND AFTER DISINTEGRATING THE MASS, SEPARATING THE ORTHO-SILICATE THUS FORMED FROM THE ZIRCONIUM OXIDE GRAINS. 